JPS62183439A - Electrophoretic display element - Google Patents
Electrophoretic display elementInfo
- Publication number
- JPS62183439A JPS62183439A JP61027263A JP2726386A JPS62183439A JP S62183439 A JPS62183439 A JP S62183439A JP 61027263 A JP61027263 A JP 61027263A JP 2726386 A JP2726386 A JP 2726386A JP S62183439 A JPS62183439 A JP S62183439A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- electrophoretic
- electrodes
- pulverized
- display element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 239000000049 pigment Substances 0.000 claims abstract description 24
- 239000002612 dispersion medium Substances 0.000 claims abstract description 22
- 239000011246 composite particle Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 125000006850 spacer group Chemical group 0.000 claims abstract description 7
- 230000002093 peripheral effect Effects 0.000 claims abstract 2
- -1 polyethylene Polymers 0.000 claims description 23
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000010419 fine particle Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 229920001038 ethylene copolymer Polymers 0.000 claims description 5
- 239000002245 particle Substances 0.000 abstract description 66
- 239000006185 dispersion Substances 0.000 abstract description 20
- 230000005484 gravity Effects 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract 2
- 238000005189 flocculation Methods 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 238000004062 sedimentation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
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- 238000004220 aggregation Methods 0.000 description 5
- 239000001045 blue dye Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000001023 inorganic pigment Substances 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- IBABXJRXGSAJLQ-UHFFFAOYSA-N 1,4-bis(2,6-diethyl-4-methylanilino)anthracene-9,10-dione Chemical compound CCC1=CC(C)=CC(CC)=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=C(CC)C=C(C)C=C1CC IBABXJRXGSAJLQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CYTCTRAEJYIZRX-UHFFFAOYSA-N (9a-hydroxy-3,5a-dimethyl-9-methylidene-2-oxo-3,3a,4,5,6,7,8,9b-octahydrobenzo[g][1]benzofuran-6-yl) acetate Chemical compound C1CC2(C)C(OC(C)=O)CCC(=C)C2(O)C2C1C(C)C(=O)O2 CYTCTRAEJYIZRX-UHFFFAOYSA-N 0.000 description 1
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 1
- JLGADZLAECENGR-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Br)Br JLGADZLAECENGR-UHFFFAOYSA-N 0.000 description 1
- QOSTVEDABRQTSU-UHFFFAOYSA-N 1,4-bis(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC)=CC=C2NC QOSTVEDABRQTSU-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 108091005944 Cerulean Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000720945 Hosta Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000001035 lead pigment Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- DNAPJAGHXMPFLD-UHFFFAOYSA-N triiodosilane Chemical compound I[SiH](I)I DNAPJAGHXMPFLD-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
孜先分互
本発明はコンピューターのディスプレイ、行先表示板、
大型表示パネル等の文字、数字、図形及び映像の可逆表
示素子、光像記憶、Ｘ線映像形成等の像情報変換素子、
又は電子黒板、再使用可能な電子シート等のソフトコピ
ーとして有用な電気泳動表示素子に関する。[Detailed Description of the Invention] The present invention relates to a computer display, a destination display board,
Reversible display elements for characters, numbers, figures, and images such as large display panels, image information conversion elements for optical image storage, X-ray image formation, etc.
The present invention also relates to an electrophoretic display element useful as a soft copy for electronic whiteboards, reusable electronic sheets, etc.
災末技Ｉ
一般に絶縁性液体中に顔料のような固体微粒子を分散さ
せると、その粒子は正又は負に帯電し、更にこの分散系
に直流電圧を印加すると、帯電粒子はその極性に応じて
陽極又は陰極に泳動する。ある色調を有する粒径０．１
〜０．３μ程度のこのような電気泳動性微粒子を前記色
調とは異なる色調に染色された高絶縁性分散媒中に分散
してなる液を、少くとも一方が透明な２枚の対向するガ
ラス電極と両電極の周縁部に配置されたスペーサーとで
形成されるセル内に封入したものは電圧印加時のセル内
粒子の移動による反射光の変化及びメモリー特性によっ
て各種機器の表示素子として利用できる。この種の表示
素子は電気泳動表示素子と呼ばれ、実際にこれをコンピ
ューターのディスプレイ、行先表示板、大型表示パネル
等の文字、数字１図形及び映像の可逆表示素子、光像記
憶、Ｘ線映像形成等の像情報変換素子、又は電子黒板、
再使用可能な電子シート等のラフ１−コピー用として利
用する提案がなされている。この゛貨気泳肋表示素子は
製造コストが安いこと、多色表示が可能であること、視
野角が広いこと等、他の表示素子にない利点を持ってい
るものの、実用面から見ると多くの欠点を持っている。Disaster Technique I Generally, when solid particles such as pigments are dispersed in an insulating liquid, the particles become positively or negatively charged. Furthermore, when a DC voltage is applied to this dispersion system, the charged particles change depending on their polarity. Migrate to the anode or cathode. Particle size 0.1 with a certain color tone
A liquid obtained by dispersing such electrophoretic fine particles of ~0.3μ in a highly insulating dispersion medium dyed in a color different from the above-mentioned color tone is placed between two opposing glasses, at least one of which is transparent. A device sealed in a cell formed by an electrode and a spacer placed around the periphery of both electrodes can be used as a display element in various devices due to changes in reflected light due to the movement of particles within the cell when voltage is applied, and memory characteristics. . This type of display element is called an electrophoretic display element, and it is actually used as a reversible display element for characters, numbers, graphics, and images on computer displays, destination display boards, large display panels, optical image storage, and X-ray images. Image information conversion element such as formation, or electronic blackboard,
Proposals have been made to use it for rough copying of reusable electronic sheets and the like. Although this ``cargo pneumatic display element'' has advantages that other display elements do not have, such as low manufacturing costs, the ability to display multiple colors, and a wide viewing angle, it has many advantages from a practical standpoint. has the disadvantages of
例えば粒子の分散安定性が悪いため、保存中或いは操作
中、セル内で粒子の凝集、沈降、電極への不可逆的付着
、マイグレーション等を起こして、表示の鮮明性及びコ
ントラストを低下させること、粒子の帯電が不明瞭であ
るため、粒子の泳動速度、従って表示速度、即ち応答速
度が遅いこと（応答時間によっては使用できる応用分野
が限定される）、同様な理由から粒子の泳動に必要な印
加電圧が高くなり、商品化が困難であること（印加電圧
が高くなると、駆動回路に汎用されているＩＣの使用が
制限されることになる。５０Ｖ以上の高耐圧ＩＣは特殊
な仕様となり、コスト的に厳しい。）等である。そして
これらの欠点を除去するため、分散液中に界面活性剤、
アルキッド樹脂、金属石ケン、オリーブ油等を添加する
試みもなされているが（例えば特公昭５２−２１８８０
号、同５６−１９６１２号）、未だ充分な効果は得られ
ていない。For example, due to poor dispersion stability of particles, during storage or operation, particle aggregation, sedimentation, irreversible adhesion to electrodes, migration, etc. may occur within the cell, reducing the clarity and contrast of the display. Because the charge is unclear, the migration speed of the particles, and therefore the display speed, that is, the response speed is slow (the application fields that can be used are limited depending on the response time).For the same reason, the application required for particle migration is slow. The higher the voltage, the more difficult it will be to commercialize the product (as the applied voltage increases, the use of general-purpose ICs for drive circuits will be restricted.High voltage ICs with a voltage rating of 50V or higher will have special specifications, resulting in higher costs). ) etc. In order to eliminate these drawbacks, surfactants,
Attempts have also been made to add alkyd resin, metal soap, olive oil, etc.
No. 56-19612), sufficient effects have not yet been obtained.
月−一一眞
本発明の目的は分散粒子である電気泳動性微粒子の分散
状態及び帯電状態を安定化又は明瞭化することにより、
粒子の凝集、沈降等を防止すると共に、低い印加電圧で
しかも速やかに粒子を泳動せしめ、こうして表示の鮮明
性、コントラスト及び応答速度を向上し、且つ商品化を
可能とした電気泳動表示素子を提供することである。The purpose of the present invention is to stabilize or clarify the dispersion state and charging state of electrophoretic fine particles, which are dispersed particles,
To provide an electrophoretic display element that prevents particle aggregation, sedimentation, etc., and allows particles to migrate quickly with a low applied voltage, thereby improving display clarity, contrast, and response speed, and which can be commercialized. It is to be.
購−ｍ一式。Purchase-m complete set.
本発明の電気泳動表示素子は第１図に示すようにある色
調を有する電気泳動性微粒子３を。The electrophoretic display element of the present invention uses electrophoretic fine particles 3 having a certain color tone as shown in FIG.
この色調とは異なる色調に染色された高絶縁性分散媒４
に分散してなる液を、少なくとも一方が透明な２枚のガ
ラス電極１，１′と両電極の周縁部内面に配置されたス
ペーサー２，２′とで形成されるセル内に封入してなる
電気泳動表示素子において、前記電気泳動性微粒子３と
して顔料微粒子表面をエチレン系共重合体又はこれとポ
リエチレンとの混合物からなる極性樹脂で被覆した複合
粒子を用いたことを特徴とするものである。Highly insulating dispersion medium 4 dyed in a color tone different from this color tone
A liquid obtained by dispersing the liquid is sealed in a cell formed by two glass electrodes 1, 1', at least one of which is transparent, and spacers 2, 2' arranged on the inner surface of the periphery of both electrodes. The electrophoretic display element is characterized in that the electrophoretic fine particles 3 are composite particles whose surfaces are coated with a polar resin made of an ethylene copolymer or a mixture of this and polyethylene.
従来の電気泳動表示素子における欠点はいずれも電気泳
動性粒子、即ち分散粒子の分散媒中での分散状態及び帯
電状態が不安定又は不明瞭であることに起因している。All of the drawbacks of conventional electrophoretic display elements are caused by the fact that the dispersion state and charging state of electrophoretic particles, ie, dispersed particles, in a dispersion medium are unstable or unclear.
分散媒中に分散した微粒子はブラウン運動媒体の流動或
いは重力のような外力によって生じる運動により互いに
衝突し、凝集する傾向がある。この場合、粒子が明瞭な
帯電を保持していれば、２つの粒子が接近してもこれら
粒子間にｉＴ７Ｉ７Ｍ反発力が生じるため、凝集を防止
することができる。また一般に分散粒子として使用され
ている顔料粒子は分散媒より重いので、経時と共に沈降
する傾向がある。このような沈降を防ぐには分散粒子の
比重を分散媒の比重と同一にするか、或いは近似させれ
ばよい。そこで顔料粒子表面に比重の小さい樹脂を被覆
することが考えられる（但し被覆後の粒径も０．１〜０
．３μ程度に抑える必要がある）。一方１分散媒中での
粒子の帯電機構については粒子表面の極性基と分散媒分
子との酸−塩基イオン結合、前記極性基と分散媒中に含
まれる微量の水分との間で生じる解離イオン、イオン性
界面活性剤を用いた場合はこの活性剤と前記極性基との
間で生じる解離イオン又はこの解離したイオンの吸着等
によると説明されている。これらはいずれも粒子表面に
イオンが存在することを前提として帯電機構を説明して
いる。Fine particles dispersed in a dispersion medium tend to collide with each other and aggregate due to movement caused by the flow of the Brownian medium or an external force such as gravity. In this case, if the particles retain a clear charge, even if two particles approach each other, iT7I7M repulsive force will be generated between these particles, so that aggregation can be prevented. Furthermore, since the pigment particles generally used as dispersed particles are heavier than the dispersion medium, they tend to settle over time. In order to prevent such sedimentation, the specific gravity of the dispersed particles may be made to be the same as or approximate the specific gravity of the dispersion medium. Therefore, it is considered to coat the surface of pigment particles with a resin having a small specific gravity (however, the particle size after coating is also 0.1 to 0.
．． (need to be kept to around 3μ). On the other hand, regarding the charging mechanism of particles in a dispersion medium, there is an acid-base ion bond between a polar group on the particle surface and a dispersion medium molecule, and a dissociated ion generated between the polar group and a trace amount of water contained in the dispersion medium. , it is explained that when an ionic surfactant is used, dissociated ions generated between the surfactant and the polar group or adsorption of the dissociated ions occur. All of these explain the charging mechanism on the assumption that ions exist on the particle surface.
そこで本発明者らは顔料粒子の表面に、化学結合によっ
てイオンを導入した極性樹脂を被覆することを考え、こ
のような極性樹脂としてエチレン系共重合体を選定した
ところ、分散粒子に明瞭、且つ安定な帯電性、及び分散
媒に近似した比重が付与され、分散粒子の凝集、沈降等
が防止できることを見出した。本発明はこのような知見
に基ずくものである。Therefore, the present inventors considered coating the surface of pigment particles with a polar resin into which ions were introduced through chemical bonds, and selected an ethylene copolymer as such a polar resin. It has been found that stable charging properties and a specific gravity similar to that of a dispersion medium are imparted, and aggregation, sedimentation, etc. of dispersed particles can be prevented. The present invention is based on such knowledge.
本発明で使用される極性樹脂はエチレンをベースとした
共重合体である。エチレンの重合体であるポリエチレン
は耐薬品性、特に耐溶剤性も成膜性も優れているため、
本発明のように分散媒中で使用する粒子の被覆には好都
合である。The polar resin used in the present invention is an ethylene-based copolymer. Polyethylene, which is a polymer of ethylene, has excellent chemical resistance, especially solvent resistance, and film-forming properties.
This is advantageous for coating particles used in a dispersion medium as in the present invention.
しかしポリエチレンは無極性樹脂であるため、分子内に
おいて電荷（イオン）が発生し難い。However, since polyethylene is a nonpolar resin, charges (ions) are difficult to generate within the molecule.
そこでこのような性質を改良するため、本発明では無極
性モノマーであるエチレンに極性上ツマ−を共重合させ
ることにより極性を付与した共重合体が用いられる。こ
こで共重合される極性上ツマ−としては酢酸ビニル、ア
クリル酸エステル、アクリル酸、メタクリル酸、無水マ
レイン酸等が挙げられる。なお本発明では極性樹脂であ
るエチレン系共重合体に無極性樹脂であるポリエチレン
を混合使用することができる。Therefore, in order to improve such properties, in the present invention, a copolymer is used in which polarity is imparted to ethylene, which is a nonpolar monomer, by copolymerizing a polar monomer. Examples of the polar polymers to be copolymerized here include vinyl acetate, acrylic esters, acrylic acid, methacrylic acid, and maleic anhydride. In the present invention, polyethylene, which is a non-polar resin, can be used in combination with the ethylene copolymer, which is a polar resin.
一方、顔料粒子としては白色系のものでは酸化チタン（
ルチル型又はアナターゼ型）、亜鉛華等の無機顔料が、
黄色系のものでは黄色酸化鉄、カドミウムイエロー、チ
タンイエロー、黄鉛等の無機顔料やハンザイエロー、ピ
グメントイエロー等の有機顔料が、赤色系のものではベ
ンガラ、カドミウムレッド等の無機顔料やシンカシャレ
ッドＹ、ホスタバームレッド等のキナクリドン顔料、パ
ーマネントレット、ファース１〜スローレッド等のアゾ
顔料等の有機顔料が、青色系顔料では群青、紺青、コバ
ルトブルー、セルリアンブルー等の無機顔料やフタロシ
アニンブルー、ファーストスカイブルー等のフタロシア
ニン顔料、インダンスレンブル−のようなインダンスレ
ン顔料等の有機顔料が、緑色系のものではクロームグリ
ーン、酸化クロム、ピリジアン等の無機顔料やピグメン
トグリーン、ナフトールグリーン等のニトロソ顔料、フ
タロシアニングリーンのようなフタロシアニン顔料等の
有機顔料が挙げられる。On the other hand, for white pigment particles, titanium oxide (
Inorganic pigments such as rutile type or anatase type), zinc white, etc.
Yellow ones include inorganic pigments such as yellow iron oxide, cadmium yellow, titanium yellow, and yellow lead, and organic pigments such as Hansa Yellow and Pigment Yellow. Red ones include inorganic pigments such as red iron oxide, cadmium red, and Shinkasha Red. Organic pigments such as quinacridone pigments such as Y, Hosta Balm Red, Permanent Ret, and azo pigments such as Firth 1 to Slow Red are used, while blue pigments include inorganic pigments such as ultramarine, navy blue, cobalt blue, and cerulean blue, and phthalocyanine blue and fast. Organic pigments such as phthalocyanine pigments such as sky blue and indanthrene pigments such as indanthremble are used; green pigments include inorganic pigments such as chrome green, chromium oxide, and pyridian, and nitrosine pigments such as pigment green and naphthol green. Examples include organic pigments such as pigments and phthalocyanine pigments such as phthalocyanine green.
次にこれら顔料粒子表面に本発明の極性樹脂を被覆する
方法について説明する。Next, a method for coating the surfaces of these pigment particles with the polar resin of the present invention will be explained.
従来、顔料のような固体粒子表面に樹脂を被用する方法
としては一般に固体粒子と樹脂とを熱時又は少量の溶媒
の存在下に混練し、冷却又は乾燥後、固化した混練物を
所望粒径に粉砕する方法が採用されている。しかしこの
方法では樹脂被覆を損なわずに粉砕するには自ずから限
界があるため（最小１μ程度）、目的とする０、１〜０
．３μ程度の粒径まで粉砕するのは困難である。そこで
本発明者らはいわゆるフラッシング法を利用して１次粒
子の形状のまま顔料粒子に樹脂を被覆する方法を考案し
た。この方法はまず顔料微粒子を高速攪拌機により少量
の水に分散してペースト状とし、一方、樹脂はその軟化
点以上に加熱した非溶媒（但し水と相溶しないもの）に
分散溶融して溶融樹脂の分散液とする。Conventionally, the method of applying resin to the surface of solid particles such as pigments is to knead the solid particles and resin under heat or in the presence of a small amount of solvent, and after cooling or drying, the solidified kneaded product is mixed into desired particles. A method of crushing into diameters is adopted. However, with this method, there is a limit to crushing without damaging the resin coating (minimum of about 1μ), so
．． It is difficult to grind down to a particle size of about 3μ. Therefore, the present inventors devised a method of coating pigment particles with a resin while maintaining the shape of the primary particles using a so-called flashing method. In this method, fine pigment particles are first dispersed in a small amount of water using a high-speed stirrer to form a paste, while the resin is dispersed and melted in a non-solvent (but not compatible with water) heated above its softening point to form a molten resin. A dispersion of
次にこの両者を混合し、高速アトライターで分散後、冷
却する。これによりペースト中の水が非溶媒中に分離す
る結果、顔料粒子表面を樹脂で被覆した複合粒子を水及
び非溶媒に分散した系が得られる。次に非溶媒として表
示用分散液の分散媒と同じものを用いた場合は前述のよ
うにして得られた分散系から水を分離し、また非溶媒と
して分散媒とは異なるものを用いた場合は分散系から水
及び非溶媒を分離した後、得られた非溶媒含有複合粒子
を常温で乾燥する（加熱乾燥すると１分散液中で凝集を
起こす恐れがある）。なお樹脂と顔料粒子との比率は主
として、前述のような理由から分散粒子である複合粒子
の比重が分散媒の比重と同−又は近似するように設定さ
れるが、同時にセルの構造、駆動の形式等も考慮する必
要がある。これらの条件も考慮すれば樹脂／顔料粒子比
（重量）は１１５〜２／１程度が適当である。Next, the two are mixed, dispersed using a high-speed attritor, and then cooled. As a result, the water in the paste is separated into the non-solvent, resulting in a system in which composite particles whose surfaces are coated with a resin are dispersed in water and the non-solvent. Next, if the same dispersion medium as the display dispersion liquid is used as the non-solvent, water is separated from the dispersion system obtained as described above, and if a different one from the dispersion medium is used as the non-solvent. After separating water and the nonsolvent from the dispersion system, the obtained nonsolvent-containing composite particles are dried at room temperature (heat drying may cause aggregation in one dispersion). The ratio of resin and pigment particles is mainly set so that the specific gravity of the composite particles, which are dispersed particles, is the same as or close to the specific gravity of the dispersion medium for the reasons mentioned above, but at the same time, the cell structure and drive It is also necessary to consider the format, etc. Taking these conditions into consideration, the appropriate resin/pigment particle ratio (weight) is about 115 to 2/1.
以上のようにして得られる本発明の複合粒子の構造モデ
ルを第２図（図中１０は顔料、１１は樹脂）に示した。A structural model of the composite particles of the present invention obtained as described above is shown in FIG. 2 (in the figure, 10 is the pigment and 11 is the resin).
なお実際に後記実施例１〜３で作った複合粒子（粒径約
０．１μ）は電子顕微鏡で観察したところ、いずれも第
２図のモデルにかなり近似していることが判った。When the composite particles (particle size: about 0.1 .mu.m) actually produced in Examples 1 to 3 described later were observed using an electron microscope, it was found that they were all quite similar to the model shown in FIG. 2.
以上のような複合粒子を分散するための分散媒としては
高絶縁性のものであればよいが、その他、高比重、且つ
低粘度で、光に対し安定で。The dispersion medium for dispersing the above-mentioned composite particles may be one with high insulating properties, but also one with high specific gravity, low viscosity, and stability against light.
毒性が少ないものが望ましい。これらの性能を備えた分
散媒の具体例としては０−ｌｍ−又はｐ−キシレン、ト
ルエン、ベンゼン、シクロヘキサン、ｎ−ヘキサン、ク
ロロブタン、クロロエタン、四塩化炭素、ケロシン、シ
クロへキシルクロライド、クロロベンゼン、１，１，２
．２−テトラクロロエチレン、三塩化弗化エタン、四弗
化二臭化エタン、四弗化二弗化エタン、沃化メチレン。It is desirable to have less toxicity. Specific examples of dispersion media with these properties include 0-lm- or p-xylene, toluene, benzene, cyclohexane, n-hexane, chlorobutane, chloroethane, carbon tetrachloride, kerosene, cyclohexyl chloride, chlorobenzene, ,1,2
．． 2-tetrachloroethylene, trichlorofluoroethane, tetrafluorodibromoethane, tetrafluorodifluoroethane, methylene iodide.
トリヨードシラン、沃化メチル、二硫化炭素等の非水溶
媒及びそれらの混合物が挙げられる。Examples include nonaqueous solvents such as triiodosilane, methyl iodide, carbon disulfide, and mixtures thereof.
これらの分散媒は染料で染色して使用される。These dispersion media are used after being dyed with a dye.
この場合、染料としては染色液の透過率をできるだけ高
くして高コントラストの表示を得るめに、分散媒に溶解
するものが選択される。このような性能を備えた染料は
油溶性染料、特に使い易さの点からアゾ染料及びアンス
ラキノン染料である。具体的には青色染料としてアンス
ラキノン系のマクロレックスブルーＲＲ（バイエル社ｍ
）、赤色染料としてアゾ系のオイルレッド５３０３ （
有水化学社製）、黒色染料としてアンスラキノン系のマ
クロレックスブルーＦＲ（バイエル社製）とアゾ系のオ
イルレッドメロ（カント−化学社製）との混合物が挙げ
られる。In this case, the dye is selected to be soluble in the dispersion medium in order to increase the transmittance of the dye solution as much as possible and obtain a high contrast display. Dyes with such performance are oil-soluble dyes, especially azo dyes and anthraquinone dyes from the viewpoint of ease of use. Specifically, as a blue dye, anthraquinone-based Macrolex Blue RR (Bayer Company m
), azo oil red 5303 (
Examples of the black dye include a mixture of anthraquinone-based Macrolex Blue FR (manufactured by Bayer) and azo-based Oil Red Mello (manufactured by Kanto Kagaku).
分散液には分散粒子の分散性及び帯電性を更に安定化又
は明瞭化して表示の鮮明性、コントラスト及び耐用時間
を改善するためにポリエチレングリコール脂肪酸エステ
ル、ソルビタン脂肪酸エステル、ポリオキシエチレング
リセリン脂肪酸エステル、ポリオキシエチレンソルビタ
ン脂肪酸エステル、ポリオキシエチレンアルキルエーテ
ル、ポリオキシエチレンアルキルフェニルエーテル、ア
ルキルエーテルカルボン酸塩、アルキルスルホン酸塩、
アルキルエーテル硫酸塩、アルキルエーテル燐酸塩等の
界面活性剤を添加することができる。The dispersion liquid contains polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, etc. in order to further stabilize or clarify the dispersibility and chargeability of the dispersed particles and improve the clarity, contrast and durability of the display. Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, alkyl ether carboxylate, alkyl sulfonate,
Surfactants such as alkyl ether sulfates and alkyl ether phosphates can be added.
なお分散液を調製する際の分散手段としては粒子表面の
樹脂被覆を損傷したり破壊しないもの、例えばペイント
シェーカーが選択使用される。ボールミルは破壊力があ
るので、使用できない。In preparing the dispersion, a dispersion means that does not damage or destroy the resin coating on the particle surface, such as a paint shaker, is selected. Ball mills cannot be used because they are destructive.
こうして得られる分散液は電気泳動表示素子用セル内に
注入される。このセルは、一方が透明なガラス電極を２
枚用意し、一方を固定し、その周縁部に、硬質樹脂粉を
混入したエポキシ接着剤をスクリーン印刷法で印刷して
付着せしめ、この電極上に他方のガラス電極を対向せし
め、接着剤を硬化させてスペーサーを形成することによ
り作られる。分散液は注射器を用いて。The dispersion liquid thus obtained is injected into a cell for an electrophoretic display element. This cell has two glass electrodes, one of which is transparent.
Prepare one sheet, fix one side, print and adhere epoxy adhesive mixed with hard resin powder to the periphery using a screen printing method, place the other glass electrode on top of this electrode, and let the adhesive harden. spacer. Dispersion using a syringe.
予め設けられた注入口から注入する。最後にこの注入口
にテフロン球を埋め込んだ後、その上を接着剤でシール
する。Inject from the injection port provided in advance. Finally, after embedding a Teflon bulb in this injection port, seal the top with adhesive.
以下に本発明を実施例によって説明する。The present invention will be explained below by way of examples.
実施例１
ポリエチレン（工作化成社製サンワックス１７１Ｐ）１
０ｇ及びエチレン−酢酸ビニル共重合体（三井デュポン
ポリケミカル社製エバフレックス２２０） １０ ｇを
混合し、これを加熱したｍ−キシレン５０ｇに分散し溶
融する。一方、アナターゼ型酸化チタン（石原産業社製
Ａ−１００）２０ｇを１００−２の水に分散した液を高
速攪拌機に入れ、激、シく混合液を冷却して溶媒層と水
層として分離した後、水層を留去することにより、酸化
チタン表面を前記混合樹脂で被覆した複合粒子を分散状
態で得た。Example 1 Polyethylene (Sunwax 171P manufactured by Koko Kasei Co., Ltd.) 1
0 g and 10 g of ethylene-vinyl acetate copolymer (Evaflex 220 manufactured by DuPont Mitsui Polychemicals) were mixed, and the mixture was dispersed in 50 g of heated m-xylene and melted. On the other hand, a solution in which 20 g of anatase-type titanium oxide (A-100 manufactured by Ishihara Sangyo Co., Ltd.) was dispersed in 100-2 water was placed in a high-speed stirrer, and the mixed solution was cooled and separated into a solvent layer and an aqueous layer. Thereafter, the aqueous layer was distilled off to obtain composite particles in which the titanium oxide surface was coated with the mixed resin in a dispersed state.
次にこの複合粒子とｍ−キシレンとアンスラキノン系青
色染料（マクロレックスブルーＲＲ）とを１．５ ：
１０ ： ０．１の重量比で混合し、ペイントシェーカ
ーで約１時間分散して表示用分散液とした。Next, this composite particle, m-xylene, and anthraquinone blue dye (Macrolex Blue RR) were mixed at 1.5:
They were mixed at a weight ratio of 10:0.1 and dispersed in a paint shaker for about 1 hour to obtain a display dispersion.
更にこの分散液を、２枚の対向する透明ガラス電極とス
ペーサーとで形成されたセル（予め注入口も設けた）の
注入口から注射器を使って注入し、注入口にテフロン球
を埋め込み、その上を接着剤でシールすることにより電
気泳動表示素子を作った。Furthermore, this dispersion was injected using a syringe through the injection port of a cell formed by two opposing transparent glass electrodes and a spacer (an injection port was also provided in advance), and a Teflon bulb was embedded in the injection port. An electrophoretic display element was made by sealing the top with adhesive.
次にこの表示素子の両電極間にＩＯＶの直流電圧を印加
すると二表示素子セル内の粒子の泳動により、速やかに
山−青の表示が行なわれた。Next, when a DC voltage of IOV was applied between both electrodes of this display element, a mountain-blue display was quickly performed due to migration of particles within the two display element cells.
この時の白色と青色との濃度（コントラス１−）比は分
光光度計（マクベス社１７Ｋｃｓ）で測定して１０であ
った。更に両電極における電圧の極性をＩＨｚの周波数
で交互に反転させて表示するテストを行なったところ、
電極への粒子の不可逆的付着もなく少くとも１０’回の
繰返し表示が可能であった。またこの表示素子は７００
時間の放置テストで粒子の凝集や沈降を生じなかった。At this time, the density (contrast 1-) ratio between white and blue was 10 as measured with a spectrophotometer (Macbeth 17Kcs). Furthermore, we conducted a test in which the polarity of the voltage at both electrodes was alternately reversed and displayed at a frequency of IHz.
Repeated display at least 10' times was possible without irreversible adhesion of particles to the electrode. Also, this display element has 700
No agglomeration or sedimentation of particles occurred in the aging test.
比較例１
表示用分散液の製造時に複合粒子の代りにアナターゼ型
酸化チタンをそのまま用いた他は実施例１と同じ方法で
電気泳動表示素子を作った。Comparative Example 1 An electrophoretic display element was produced in the same manner as in Example 1, except that anatase-type titanium oxide was used as it was instead of composite particles during the production of a display dispersion.
このものはＩＯＶの直流電圧の印加で白−青の表示は可
能であったが（但し実施例１の場合よりも表示速度は遅
い）、ｆ８．正極性の交互反転による表示テストでは数
回の繰返しで一部の粒子が凝集したり、電極に不可逆的
に付着して泳動しない部分が生じて表示不能となった。This device was able to display white and blue by applying a DC voltage of IOV (however, the display speed was slower than in Example 1), but f8. In a display test in which the positive polarity was alternately reversed, after several repetitions, some of the particles agglomerated or irreversibly adhered to the electrode, resulting in areas that did not migrate, making it impossible to display.
また放置テストでは２０時間で沈降が生じ、使用不能と
なつた・
比較例２
複合粒子の製造時にエチレン−酢酸ビニル共重合体を用
いなかった他は実施例１と同じ方法で電気泳動表示素子
を作った。しかしこの素子の場合はＩＯＶの直流電圧を
印加しても殆どの粒子の泳動が見られなかった。そして
印加電圧を１００Ｖに上げたところ１粒子の泳動が可能
となり、実施例の場合よりも表示速度は遅いものの白−
青の表示が行なわれた。しかし１００■の電圧極性の交
互反転による表示テストでは１０’回の繰返しで一部粒
子の凝集や電極への不可逆的付着が生じた。また放置テ
ストでは１００時間で沈降を生じた。In addition, in the standing test, sedimentation occurred after 20 hours, making it unusable. Comparative Example 2 An electrophoretic display element was produced in the same manner as in Example 1, except that the ethylene-vinyl acetate copolymer was not used during the production of the composite particles. Had made. However, in the case of this element, almost no particles were observed to migrate even when a DC voltage of IOV was applied. When the applied voltage was increased to 100V, it became possible to migrate one particle, and although the display speed was slower than in the example, the white -
A blue display was made. However, in a display test in which the voltage polarity was alternately reversed for 100 times, some particles agglomerated or irreversibly adhered to the electrodes after 10' repetitions. In addition, in a standing test, sedimentation occurred after 100 hours.
実施例２
複合粒子の製造時に、ポリエチレンとしてＢＡＳＦ社製
Ａ−ｗａｘを、エチレン−酢酸ビニル重合体として三井
デュポンポリケミカル社製エバフレックス４２０を、ま
たアナターゼ型酸化チタンの代りにルチル型酸化チタン
（チタン工業社製ＫＲ３１０）を夫々用いると共に、表
示用分散液の製造時にアンスラキノン系青色染料の代り
にアゾ系赤色染料（オイルレッド５３０３）を用いた他
は実施例１と同じ方法で電気泳動表示素子を作った・
次にこの表示素子の性能を実施例１と同じ方法で評価し
た。即ちまず両電極にＩＯＶの直流電圧を印加すると、
表示セル中の粒子の泳動により速やかに白−赤の表示が
行なわれた。この時の白色と赤色との濃度比は７であっ
た。また電圧極性の交互反転による表示テストでは実施
例１と同様、電極への不可動的付着もなく、少くとも１
０６回の繰返し表示が可能であった。更に放置テストで
は実施例１と同様に良好な結果が得られた。Example 2 During production of composite particles, A-wax manufactured by BASF was used as polyethylene, Evaflex 420 manufactured by DuPont Mitsui Polychemicals was used as the ethylene-vinyl acetate polymer, and rutile titanium oxide (rutile titanium oxide) was used instead of anatase titanium oxide. Electrophoretic display was carried out in the same manner as in Example 1, except that azo-based red dye (Oil Red 5303) was used instead of anthraquinone-based blue dye during production of the display dispersion. The device was manufactured.Next, the performance of this display device was evaluated using the same method as in Example 1. That is, when a DC voltage of IOV is first applied to both electrodes,
A white-red display was quickly performed due to the migration of particles in the display cell. The density ratio between white and red at this time was 7. Furthermore, in the display test using alternating reversal of voltage polarity, as in Example 1, there was no immovable adhesion to the electrodes, and at least one
It was possible to repeat the display 06 times. Furthermore, in the standing test, good results were obtained as in Example 1.
実施例３
複合粒子の製造時にサンワックス１７１ Ｐポリエチレ
ン１０ｇの代りにアライドケミカル社製ＡＣ−７１５ポ
リエチレン１５ｇを、エチレン−酢酸ビニル共重合体Ｌ
ｏｇの代りにエチレン−酢酸ビニル〜アクリル酸グラフ
ト共重合体（試作品）５ｇを、またアナターゼ型酸化チ
タン２０ｇの代りにルチル型酸化チタン（石原産業社製
Ｒ−８２０）４０ｇを夫々用いると共に、表示用分散液
の製造時にｍ−キシレンの代りにトリクロロトリフルオ
ロエタンを、またアンスラキノン系青色染料（マクロレ
ックスブルーＲＲ）の代りにモノアゾ系赤色染料（オイ
ルレッド）とアンスラキノン系青色染料（マイクロレス
ブルーＦＲ）との１：１（重量）混合物を夫々用い、且
つ複合粒子とトリクロロトリフルオロエタンと前記染料
混合物とを２０ ： １０ ： ０．１５の重量比で混
合した他は実施例１と同じ方法で電気泳動表示素子を作
った。Example 3 During production of composite particles, 15 g of AC-715 polyethylene manufactured by Allied Chemical Co., Ltd. was substituted for 10 g of Sunwax 171 P polyethylene, and 15 g of ethylene-vinyl acetate copolymer L was used instead of 10 g of Sunwax 171 P polyethylene.
Using 5 g of ethylene-vinyl acetate-acrylic acid graft copolymer (prototype) instead of OG, and 40 g of rutile-type titanium oxide (R-820 manufactured by Ishihara Sangyo Co., Ltd.) instead of 20 g of anatase-type titanium oxide, When manufacturing display dispersion liquid, trichlorotrifluoroethane was used instead of m-xylene, and monoazo red dye (Oil Red) and anthraquinone blue dye (Micro) were used instead of anthraquinone blue dye (Macrolex Blue RR). Example 1 except that a 1:1 (by weight) mixture with Les Blue FR) was used, and the composite particles, trichlorotrifluoroethane, and the dye mixture were mixed in a weight ratio of 20:10:0.15. An electrophoretic display element was made using the same method.
次にこの表示素子の性能を実施例１と同じ方法で評価し
た。即ちまず両電極にＩＯＶの直流電圧を印加すると、
表示セル中の粒子の泳動により速やかに白−黒の表示が
行なわれた。この時の白色と黒色との濃度比は１０であ
った。また電圧極性の交互反転による表示テストでは実
施例１と同様に良好な結果が得られた。Next, the performance of this display element was evaluated using the same method as in Example 1. That is, when a DC voltage of IOV is first applied to both electrodes,
The electrophoresis of particles in the display cell quickly produced a black-and-white display. At this time, the density ratio between white and black was 10. Also, in a display test using alternate reversal of voltage polarity, good results were obtained as in Example 1.
効 果
以上の如く本発明の電気泳動表示素子は分散粒子として
顔料微粒子表面をエチレン系共重合体を含む極性粒子で
被覆した複合粒子を用いたので、従来の顔料微粒子単独
の粒子系に比べて分散性及び帯電性が安定化又は明瞭化
し、その結果、保存中或いは操作中１粒子の凝集、沈降
、電極への不可逆的付着等を防止すると共に、低い印加
電圧でしかも速やかに粒子を泳動せしめ、こうして表示
の鮮明性、コントラスト及び応答速度を向上し、且つ商
品として実用化を可能とした。Effects As described above, the electrophoretic display element of the present invention uses composite particles whose surfaces are coated with polar particles containing an ethylene copolymer as dispersed particles. Dispersibility and chargeability are stabilized or clarified, and as a result, particles can be prevented from agglomeration, sedimentation, irreversible adhesion to electrodes, etc. during storage or operation, and particles can be migrated quickly with low applied voltage. In this way, the clarity, contrast, and response speed of the display were improved, and it became possible to put it into practical use as a commercial product.
第１図は本発明の電気泳動表示素子の一例の断面図、第
２図はこの表示素子に用いられる電気泳動性微粒子の断
面図である。
１．１′・・・ガラス電極 ２，２′・・・スペ
ーサー３・・・電気泳動性微粒子 ４・・・分散媒
１０・・・顔料粒子 １１・・・極性樹脂ｉ
２■FIG. 1 is a sectional view of an example of an electrophoretic display element of the present invention, and FIG. 2 is a sectional view of electrophoretic fine particles used in this display element. 1.1'... Glass electrode 2,2'... Spacer 3... Electrophoretic fine particles 4... Dispersion medium 10... Pigment particles 11... Polar resin i
2■
Claims (1)
異なる色調に染色された高絶縁性分散媒に分散してなる
液を、少なくとも一方が透明な２枚のガラス電極と両電
極の周縁部内面に配置されたスペーサーとで形成される
セル内に封入してなる電気泳動表示素子において、前記
電気泳動性微粒子として顔料微粒子表面をエチレン系共
重合体又はこれとポリエチレンとの混合物からなる極性
樹脂で被覆した複合粒子を用いたことを特徴とする電気
泳動表示素子。1. A liquid obtained by dispersing electrophoretic fine particles having a certain color tone in a highly insulating dispersion medium dyed in a color different from this color tone is applied to two glass electrodes, at least one of which is transparent, and the peripheral edges of both electrodes. In an electrophoretic display element enclosed in a cell formed by a spacer disposed on the inner surface, the surface of the pigment fine particles as the electrophoretic fine particles is made of a polar resin made of an ethylene copolymer or a mixture of this and polyethylene. An electrophoretic display element characterized by using composite particles coated with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61027263A JPS62183439A (en) | 1986-02-07 | 1986-02-07 | Electrophoretic display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61027263A JPS62183439A (en) | 1986-02-07 | 1986-02-07 | Electrophoretic display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62183439A true JPS62183439A (en) | 1987-08-11 |
Family
ID=12216185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61027263A Pending JPS62183439A (en) | 1986-02-07 | 1986-02-07 | Electrophoretic display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62183439A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003167279A (en) * | 2001-09-21 | 2003-06-13 | Bridgestone Corp | Particle for image display and image display device |
| JP2003167274A (en) * | 2001-09-19 | 2003-06-13 | Bridgestone Corp | Particle for image display, and image display device |
| JP2003177433A (en) * | 2001-09-21 | 2003-06-27 | Bridgestone Corp | Particle for image display and image display device |
| JP2003248247A (en) * | 2001-12-17 | 2003-09-05 | Bridgestone Corp | Image display |
| JP2004527776A (en) * | 2000-09-08 | 2004-09-09 | キャボット コーポレイション | Electrophoretic display containing modified particles |
| US6822782B2 (en) | 2001-05-15 | 2004-11-23 | E Ink Corporation | Electrophoretic particles and processes for the production thereof |
| JP2007192945A (en) * | 2006-01-17 | 2007-08-02 | Seiko Epson Corp | Electrophoresis display sheet, electrophoresis display device, and electronic apparatus |
| JP2008542809A (en) * | 2005-05-27 | 2008-11-27 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Robust multiparticulate system for color electrophoretic displays with very low drive voltage with small amounts of electrolyte |
| US7525719B2 (en) | 2001-09-19 | 2009-04-28 | Bridgestone Corporation | Particles and device for displaying image |
| JP2010282220A (en) * | 2010-07-30 | 2010-12-16 | Ricoh Co Ltd | Display liquid for electrophoresis display, and electrophoresis display medium |
| JP2014021176A (en) * | 2012-07-13 | 2014-02-03 | Seiko Epson Corp | Electrophoretic material, electrophoretic display device, and electronic apparatus |
-
1986
- 1986-02-07 JP JP61027263A patent/JPS62183439A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004527776A (en) * | 2000-09-08 | 2004-09-09 | キャボット コーポレイション | Electrophoretic display containing modified particles |
| US6822782B2 (en) | 2001-05-15 | 2004-11-23 | E Ink Corporation | Electrophoretic particles and processes for the production thereof |
| JP2003167274A (en) * | 2001-09-19 | 2003-06-13 | Bridgestone Corp | Particle for image display, and image display device |
| US7525719B2 (en) | 2001-09-19 | 2009-04-28 | Bridgestone Corporation | Particles and device for displaying image |
| JP2003167279A (en) * | 2001-09-21 | 2003-06-13 | Bridgestone Corp | Particle for image display and image display device |
| JP2003177433A (en) * | 2001-09-21 | 2003-06-27 | Bridgestone Corp | Particle for image display and image display device |
| JP2003248247A (en) * | 2001-12-17 | 2003-09-05 | Bridgestone Corp | Image display |
| JP2008542809A (en) * | 2005-05-27 | 2008-11-27 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Robust multiparticulate system for color electrophoretic displays with very low drive voltage with small amounts of electrolyte |
| JP2007192945A (en) * | 2006-01-17 | 2007-08-02 | Seiko Epson Corp | Electrophoresis display sheet, electrophoresis display device, and electronic apparatus |
| JP2010282220A (en) * | 2010-07-30 | 2010-12-16 | Ricoh Co Ltd | Display liquid for electrophoresis display, and electrophoresis display medium |
| JP2014021176A (en) * | 2012-07-13 | 2014-02-03 | Seiko Epson Corp | Electrophoretic material, electrophoretic display device, and electronic apparatus |
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